1. Technical Field
The present invention relates to a laminated glass and a manufacturing method of the same widely applied to window materials of buildings, and window materials of automobiles, trains, and airplanes, and more specifically relates to the heat ray shielding laminated glass and the manufacturing method of the same not requiring high temperature/high pressure processing by an autoclave, which can be manufactured under a room temperature, and using composite tungsten oxide particles and/or hexaboride particles having low haze and excellent design property, while having an excellent heat ray shielding performance.
2. Description of Related Art
A safety glass applied to window materials of automobiles, etc, is proposed, for the purpose of reducing a cooling load and a human heat feeling, by interposing a heat ray shielding film between plate glasses and shielding a solar energy that enters from this glass.
For example, patent document 1 discloses a laminated glass in which a soft resin layer containing a heat ray shielding metal oxide composed of tin oxide or indium oxide with particle size of 0.1 μm or less is interposed between a pair of plate glasses. Patent document 2 discloses a laminated glass in which an intermediate layer with metals of Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, Mo, oxide, nitride, and sulfide of them or doped objects of Sb and F or composite materials of them dispersed therein, is provided between at least two plate glasses. Patent document 3 discloses a laminated glass for automobiles in which ultrafine particles composed of TiO2, ZrO2, SnO2, In2O3, and glass fiber composed of organosilicon or organosilicon compound are interposed between transparent plate-like members. Patent document 4 proposes a laminated glass in which an intermediate layer composed of three layers is provided between at least two transparent glass plate-like bodies, and metals of Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, Mo, oxide, nitride, and sulfide of them and doped objects of Sb and For composite materials of them are dispersed in a second layer of the intermediate layer, with the intermediate layer between the first layer and the third layer set as a resin layer.
However, in the inventions of patent documents 1 to 4, large quantities of particles having heat ray shielding performance need to be added, to secure the heat ray shielding performance. As a result, there is a problem that a visible light transmission performance is deteriorated, with an increase of an addition of the particles having the heat ray shielding performance. However, if the addition of the particles having the heat ray shielding performance is reduced, although the visible light transmission performance is increased, the heat ray shielding performance is deteriorated this time. After all, there is a problem that it is difficult to simultaneously satisfy the heat ray shielding performance and the visible light transmission performance.
Under such a background of the technique, the following two kinds of heat ray shielding laminated glasses are already disclosed by inventors of the present invention.
(1) Patent document 5 discloses the heat ray shielding laminated glass formed by interposing the intermediate layer having the heat ray shielding performance between two plate glasses, wherein the intermediate layer is constituted of a vinyl resin intermediate film containing hexaboride particles alone, or hexaboride particles and ITO particles and/or ATO particles.(2) Patent document 6 discloses the heat ray shielding laminated glass, with a heat ray shielding film containing the aforementioned particles formed therein, and further having vinyl resin as an intermediate film between the aforementioned two plate glasses.
Further, patent document 7 discloses the heat ray shielding laminated glass formed by interposing the intermediate layer having the heat ray shielding performance between two plate glasses, wherein the intermediate layer contains particles of the composite tungsten oxide expressed by a general formula MxWyOz (wherein W is tungsten, O is oxygen, satisfying 0.001≦x/y≦1, 2.0≦z/y≦3.0) and vinyl resin.
(Patent document 1)
    Japanese Patent Laid Open Publication No. 08-217500(Patent document 2)    Japanese Patent Laid Open Publication No. 08-259279(Patent document 3)    Japanese Patent Laid Open Publication No. 04-160041(Patent document 4)    Japanese Patent Laid Open Publication No. 10-297945(Patent document 5)    Japanese Patent Laid Open Publication No. 2001-89202(Patent document 6)    Japanese Patent Laid Open Publication No. 2004-338963(Patent document 7)    WO2005/87680
The heat ray shielding laminated glass having the intermediate layer containing composite tungsten oxide particles and hexaboride particles between two plate glasses is manufactured by kneading dispersion liquid of the composite tungsten oxide particles and hexaboride particles, a plasticizer, and a vinyl resin by using an extruder, a plastograph, a kneader, a Banbury mixer, and a Calendar roll, etc, then sheet-like molding them by an extrusion method, a Calendar method, and a press method, etc, to thereby obtain the heat ray shielding intermediate film, and interposing the heat ray shielding intermediate film between two plate glasses, with the heat ray shielding intermediate film subjected to processing at high temperature and under high pressure by using the autoclave. In the heat ray shielding laminated glass, the composite tungsten oxide or the hexaboride particles are not formed into aggregates but are set in a state in which a uniform dispersability is maintained. As a result, a satisfactory heat shielding laminated glass having an excellent heat shielding performance and a low haze value, can be obtained.
Here, the inventors of the present invention achieves a technique that by replacing the vinyl resin between two glass plates with ultraviolet ray curing resin, a kneading operation by using the aforementioned extruding machine, plastograph, kneader, Banbury mixer, and Calendar roll, etc, and a sheet-like molding operation by using the extrusion method, Calendar method, and press method, etc, and a operation at high temperature under high pressure, can be omitted, thus making it possible to improve productivity and reduce a production cost.
However, when the vinyl resin between the two glass plates is replaced with ultraviolet ray curing resin, a new problem is found out.
Namely, when the composite tungsten oxide particles or the hexaboride particles are dispersed into the laminated glass manufactured by irradiation of ultraviolet ray after an ultraviolet ray curing resin precursor is filled between two glass plates, anew problem is found out. Specifically, this new problem is that although the laminated glass manufactured by the aforementioned method and finally obtained has an excellent heat ray shielding function, haze (cloudiness) becomes higher and the design property is deteriorated. Here, from the viewpoint of design property, it is a matter of course that a low haze is requested even in the laminated glass.